Polyazo dyestuffs



Patented Mar. 23, 1954 UNITED STATES PATENT POLYAZO DYESTUFFS No Drawing. Application June 20, 1951, Serial No. 232,662

Claims priority, application Switzerland June 23, 1950 12 Claims. (Cl. 260--144) OFFICE The present invention relates to new polyazo dyestuiis and to the preparation thereof.

Dyes which yield yellow, orange and brown shades in textile dyeings are known. However, these known dyes, in so far as they are characterized by good fastness to light, are bound up with poor dischargeability or, when their dischargeability is good, suffer'from poor fastness to light.

A primary object of the present invention is the embodiment of a new series of dyes of the said class-yellow, orange and brown-which are characterized by the fact that, in addition to. the purity of shade of the dyeings produced therethe present invention comprise the dichlorides and dibromides of fumaric acid, maleic acid, citraconic acid and mesaconic acid.

The new dyestuffs, which correspond to the general formula with, such dyeings possess both good fastness to light and also good dischargeability.

This and other objects which will hereinafter appear are realized by the present invention according to which, briefly stated, the desired dyestuffs are prepared by condensing 2 mols of an aminoazo dyestuif which corresponds to the formula wherein each of a: and y is one of the numerals 0 and 1, and each of R1, R2, R3 and R4 stands for a radical of the benzene or naphthalene series, which may be substituted, as for example by halogen atoms or by lower alkyl, lower alkoxy, acylamino or nitro groups, and which in toto carry at least two solubilizing groups, such as -SOsH and/or -COOH, with 1 mol of a dicarboxylic acid halide which corresponds to the formula wherein Y stands for H or H3, and Z stands for C1 or Br, the condensation being carried out in the presence of an acid-binding agent.

The joining together of the two molecules of aminoazo dyestuff by means of the dicarboxylic acid halide takes place preferably at room temperature (about C.) in a weakly acid (acetic acid), neutral or alkaline aqueous medium. The liquid dihalide or a solution thereof in an organic wherein each of a: and y is one of the numerals 0 and 1, Y stands for H or CH3, and each of R1,

R2, R3 and R4 stands for a radical of the benzene or naphthalene series, such radicals in toto carrying at least two solubilizing groups, such as -SO3H and COOH, and being otherwise unsubstituted or substituted by one or more halogen atoms or lower alkyl, lower alkoxy, acylamino or nitro groups, dye cotton and regenerated cellulose in pure yellow, orange or brown shades, the resultant dyeings possessing good dischargeability and good fastness to light.

The following examples set forth representative exemplary embodiments of the invention, and these examples are intended to be solely illustrative and not at all limitative. In these examples, parts are by weight.

Example 1 464 parts of the dyestufi prepared by coupling diazotized Z-aminonaphthalene 4,8 disulfonic acid with 3-acetylamino-l-aminobenzene are meme 3 added, stirring is continued until no more free filtered off and dried. The thus-obtained dyeamino group can be detected. Thereupon the stuff is a brown-red powder which corresponds formed dyestuff is separated out with the aid of to the formula.

B 0311 CH:

common salt (sodium chloride) while warming and which dyes cotton and regenerated cellulose slightly, and the precipitated dyestufi isolated in yellow-orange shades of very good dischargeby filtering and then dried. l ability and fastness to, light.

It is a brownish yellow powder, which corre- Dyestufis of similar properties are obtained sponds to the formula when, in the starting dyestuff of this example,

so3H IIIHCOCHa V SO3H N=N NH o o-( m SOzH (This formula may show only the chemical combination but not the structural configuration) and dyes cotton and regenerated cellulose .in yelthe 1-amino-3-methylbenzene is replaced by one low shades which are of very good dischargeof'the amines of the benzene series enumerated ability and very good iastness to light. in Example 1. I

Dyestuffs of similar properties are obtained By replacing the f-u'ma'ric acid dichloride by by replacing in 'the starting dyestuff of this exan equivalent amount of maleic acid dichloride ample, on the one hand the 2-aminonaphthaleneor maleic acid dibromide, and otherwise proceed- 4,8-disulf0nic acid by an equivalent quantity of ing as described in the present example, cotton another aminonaphthalene=disulfonic acid such, dyestuifs of the same properties as the initially for example, as 2-aminonaphthalene-6,8-disuldescribed dyestufi are obtained. ionic acid or2-aminonaphthalene-5,7-disulfonic Example 3 acid, etc., and/or on the other hand replacing the 3-acetylamino-l-aminobenzene by an equiv- 569 part Of the y tu 0f the formula alent quantity of another amine of the benzene soar: v 0011, series, such for example as aniline, 2-amino-1- I 1 methylbenzene, 3 amino 1 methylbenzene, 1- =N qqqqONH; amino 3 'ethylbe'nzen'e, 1-"amino-2,5-dimethyl- I benzene, 1-amino-2-methoxybenzene, l-amin'o- 0 1105s 7 0H: CH;

2-methoxy-5-acetylamii1obenzene, l-amino-2,5- dime'thoxybenzene,1-amino-2;5-diethoxybenzene, prepared by coupling diazotized -2'-am'inonaph- 1 -amino 3 -formylaminobenzene, 1-amino-3- thalene-6,8-disulfonic acid with 1-amino-3- benzoylaminob'enzene, =etc., whileotherwise promethylbenzene, diazotization of the resultant ceeding according to the prescriptions of the :examinoazo dyestuff, and coupling of the latter ample. with 1-amino-2-methoxy 5emethy1benzene, are

It, in any of the preceding indicated em dissolved in waterat room temperature withadbodiments, the fumaric acid dichloride is replaced dition of sodium hydroxide solution to maintain byfumaricacid dibromide,the'identical dyestufi neutrality. Into the thus-obtained neutral dyeis produced in each case. stuff solution, .there are simultaneously added dropwise and with thorough stirring a solution Example 2 i of 76.5 parts of fumaric acid dichloride in so 475 parts of the dyestuh prepared by coupl-in parts of benzene and a suflicient amount of sodiazotized 4 amino-l,1"-azobenzene-3A"-disuldium carbonate solution to keep the reactionronfonic acid with 1-amino-3-methylbenzene are stantly weakly alkaline.

dissolved in water at room temperature, sodium After all the fumaric acid dichloride-has been hydroxide solution being added to keep the dyeadded, stirringof the solution is continued until stuff solution neutral. Into the said dyestuff no more free. amino group can be detected.

solution, there are simultaneously added drop- Thereupon the formed dyestufi is salted out with wise and while stirring thoroughly a solution of the aid of sodium chloride while warming 76.5 parts of fumaric acid dichloride in parts slightly. The precipitated dyestuff .is then .fil-

of benzene and a solution of sodium carbonate, tered off and dried. the latter in such quantity as constantly to main- The thus-prepared dyestufi is a brown-yellow tain the reaction weakly alkaline. powder which corresponds .tothe formula.

soul on; can:

N=NON=N x 0- on: 5 H038 pm After all the fumaric acid dichloride has been and which dyes cotton and regenerated cellulose added, the resultant solution is further stirred in orange shades of very good -'dischargeability until no more free amino group can be detected. and fastness to light. Thereupon the formed dyestufl'is salted {out while Dyestufis with similar properties are obtained warming slightly, and the separated dyestufi 7:5 by replacing in'the startin'g dyestdfi-o'f this ample, on the one hand theZ-aminonaphthalene- 6,8-disulfonic acid by an equivalent quantity of 2-aminophthalene-4,8-disulfonic acid or of 2- aminonaphthalene-5,7-disulfonic acid and/or on the other hand replacing the 1-amino-3-methyl- SOaH CH5 HOa Ewample 4 636 parts of the dyestuff of the formula prepared by coupling diazotized 4-amino-1,1- azobenzene-3A'-disulfonic acid with l-amino- 3-methylbenzene, diazotizing the thus-prepared aminodisazo dyestuif and then coupling it with 1-amino-3-acetylaminobenzene, are dissolved in water at -40 C. while maintaining the neutrality of the resultant solution by the addition of sodium hydroxide solution. 76.5 parts of fumaric acid dichloride are then added, together with sodium carbonate. Stirring of the reaction mixture is continued until the presence of a free amino group can no longer be detected, whereupon the newly-formed dyestuff is precipitated with the aid of sodium chloride and while warming. The precipitated dyestuff is then filtered off and dried to produce a dark brown powder which corresponds to the formula SO|H CH:

and which dyes cotton and regenerated cellulose in brown shades of good dischargeability and fastness to light.

Dyestuffs of similar properties are obtained when, in the initial dyestuff of this example, the 1-amino-3-acetylaminobenzene and/or the 1- amino-3-methy1benzene is replaced by an equiv alent quantity of one of the amines of the bene otherwise proceeding according to the prescriptions of the present example.

Example 5 594 parts of the dyestufl of the formula son: on,

SOsH

prepared by coupling diazotized 4-amino-l,1'- azobenzene-3,4-disulfonic acid with 1-amino-3- methylbenzene, and acylating the thus-obtained aminoazo dyestuif with p-nitrobenzoyl chloride, followed by reduction of the nitro group to the amino group, are dissolved in water at room temperature, with addition of sodium hydroxide solution to keep the dyestufi solution neutral. Thereupon 76.5 parts of fumaric acid dichloride, together with sufilcient sodium bicarbonate to maintain the reaction weakly alkaline, are added, and the mixture stirred until free amino groups have entirely disappeared. The newly-formed dyestuil is then precipitated with the aid of sodium chloride and while warming slightly, and

NHCOGH;

the precipitated dyestuff is then filtered off and dried. The resultant yellow brown powder corresponds to the formula and dyes cotton and regenerated cellulose in yellow shades of good dischargeability and fastness to light.

Dyestufis with similar properties are obtained when, in the starting dyestuif of this example, on the one hand the 4-amino-1,1'-aZo-benzene- 3,4=-disu1fonic acid is replaced by the equivalent quantity of an aminoazo compound prepared by coupling diazotized 2-aminonaphthalene-4B-disulfonic acid with one of the amines of the benzene series enumerated in Example 1 and/or on the other hand the 1-amino-3-methylbenzene is replaced by an equivalent quantity of one of the NHCOCH! Y said amines, while otherwise adhering to the zene series enumerated in Example 1, and while replacement in the case of the first paragraph of the present example, the obtained dyestufi will correspond to the formu a H 8 V V in brown shades of good dischargeability and very good light fastness.

'(This formula may show only the chemical combination but not the structural configuration.)

Example 6 525 parts of the dyestuff of the formula prepared by coupling diazotized l-aminobenzene--sulfonic acid with l-amino-naphthalene- 6-sulfonic acid, diazotizing the obtained aminoazo dyestufi and coupling the resultant diazo compound with l-amino-B-methylbenzene, are dissolved in water at room temperature, sodium hydroxide solution being added to maintain the neutrality of the dyestuff solution. Thereupon 76.5 parts of fumaric acid dichloride are added,

together with sufficient sodium carbonate to keep the reaction weakly alkaline.

' As soon as no free amino group can be detected, the newly-formed dyestufi is precipitated by means of sodium chloride and while warming, whereupon the precipitated dyestuff is filtered off and dried. In this way, the dye stuff is obtained in the form of a brown powder, which corresponds to the formula and which dyes cotton and regenerated cellulose Dyestuffs with similar properties are obtained when, in the starting dyestuff of this example, on the one hand the l-aminobenzene-l-sulfonic acid is replaced by an equivalent quantity of l-amino- 2,4-dichlorobenzene-G-sulfonic acid, l-amino-lbromobenzene-2-sulfonic acid, 1-amino-4-nitrobenzene-Z-sulfonic acid or l-amino-Z-carboxybenzene-S-sulfonic acid, and/or on the other hand the 1-amino-3-methylbenzene is replaced by one of the amines of the benzene series enumerated in' Example 1, and while otherwise adhering to the prescriptions of the present example.

Analogous dyestuff are also obtained when, in the starting dyestuffs of this example, the 1- aminobenzene-l-sulfonic acid is, on the one hand, replaced by an equivalent quantity of l-aminobenzene-2,5-disulfonic acid, and the l-aminonaphthalene-S-sulfonic acid is, on the other hand, replaced by l-aminonaphthalene.

Dyestuffs of the same properties are obtained when the iumaric acid dichloride is replaced by an equivalent quantity of maleic acid dichloride, while dyestuffs of similar properties are obtained when the fumaric acid dichloride is replaced by an equivalent quantity of citraconic acid dichloride.

2 In this Way it is possible to prepare inter alia dyestuffs which correspond to the formulae C O 0H s (I) C'IHii NHCO aqueous medium and in presence of an acid-bind- 10 ing agent, two mols of an aminoazo dyestuff corresponding to the formula wherein each of :1: and y is one of the numerals 0 and 1, and wherein each of R1, R2, R3 and R4 stands for a radical selected from the group consisting of unsubstituted and halogen-substituted, lower alkyl substituted, lower alkoxy-substituted, acylamino-substituted and nitro-substituted radicals of the benzene and naphthalene series, such 10 ing agent, two mols "of the aminoazo dyestuif corresponding to the formula SOaH (IJH;

with one mol of fumaric acid dichloride.

4. A process of manufacture of a polyazo dyestuff comprising the step of condensing, in an aqueous medium and in presence of an acidbinding agent, two mols of the aminoazo dyestuif corresponding to the formula SOsH CH2 5 .W MGNH.

H O 3 S with one mol of fumaric acid dichloride.

5. A process of manufacture of a polyazo dyestufi comprising the step of condensing in an aqueous medium and in presence of an acid-binding agent, two mols of the aminoazo dyestuff corresponding to the formula SOaH CH3 lIVHGOCHa radicals possessing together at least two solubiliz- 30 with one mol of fumaric acid dichloride.

ing groups with one mol "of a dicarboxylic acid halide corresponding to the general formula wherein Y stands for a member selected from the group consisting of hydrogen and methyl, and Z stands for an atom selected from the group consisting of chlorine and bromine.

2. A process of manufacture of a polyazo dyestuff comprising the step of condensing, in an aqueous medium and in presence of an acid- 6. A process of manufacture of a polyazo dyestuff comprising the step of condensing, in an aqueous medium and in presence of an acidbinding agent, two mols of the aminoazo dyestui'f 35 corresponding to the formula with one mol of fumaric acid dichloride.

7. A polyazo dyestuff corresponding to the formula binding agent, two mols of the aminoazo dyestuif corresponding to the formula SOaH NHCOCH;

S OaH with one mol of fumaric acid dichloride.

3. A process of manufacture of a polyazo dye- SIOsH stuff comprising the step of condensing, in an aqueous medium and in presence of an acid-bind- NHOOOH:

SOIH

9. The polyazo dyestuif corresponding to the formula CH3 @NHO 0-0 H:

10. The polyazo dyestuif corresponding to the formula,

CH: I

son;

11. The polyazo dyestufl corresponding to the formula HOaS soln on, NHCOCH; N= 1 I 12. The polyazo dyestuff corresponding to the NONE) ocH= formula,

HO;S'C N= N=NQNHCO-CH= CHI PH. GRANDJEAN.

WALTER WEI-IRLI.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date I 1,940,683 Jordan Dec; 26, 1933 2,104,595 Schirm Jan. 4, 1938 

11. THE POLYAZO DYESTUFF CORRESPONDING TO THE FORMULA 